JP6863975B2 - Thermoplastic resin composition and molded products containing it - Google Patents

Description

The present invention relates to a thermoplastic resin composition and a molded product containing the same. More specifically, the present invention relates to a thermoplastic resin composition having excellent flame retardancy, transparency, rigidity, heat resistance, etc., and a molded product containing the same.

Polycarbonate resin is an engineering plastic having excellent mechanical strength, heat resistance, transparency and the like. The polycarbonate resin is used in various fields such as office automation equipment, electrical / electronic products, and building materials. Of these, in order for the polycarbonate resin to be applied to transparent exterior materials for electrical / electronic products, high flame retardancy and transparency are required, and slimming down electrical / electronic products such as televisions, monitors, and laptop computers. And with the thinning, high rigidity is required.

In order for the thermoplastic resin composition containing the polycarbonate resin to realize excellent flame retardancy, rigidity, etc., in addition to the polycarbonate resin, a dripping inhibitor such as a fluorinated polyolefin resin, a filler such as glass fiber, etc. are used. Although it must be applied, if an excessive amount of anti-dripping agent, filler, etc. is used to realize flame retardancy, rigidity, etc. suitable for thin-film exterior materials, etc., the transparency and impact resistance of the thermoplastic resin composition , Workability may decrease.

Therefore, it is required to develop a thermoplastic resin composition which is excellent in flame retardancy, transparency, rigidity, heat resistance, and balance of these physical properties, and can be applied to a thin film type exterior material or the like.

The background technique of the present invention is disclosed in Korean Patent Publication No. 2014-090465.

An object of the present invention is to provide a thermoplastic resin composition excellent in flame retardancy, transparency, rigidity, physical balance of these properties, and a molded product containing the same.

Another object of the present invention is to provide a thermoplastic resin composition having excellent heat resistance and the like, and a molded product containing the same.

The above object and other objects of the present invention can all be achieved by the present invention described below.

One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition is a polycarbonate resin; a siloxane copolymer containing a repeating unit represented by the following formula 1 and a repeating unit represented by the following formula 2; an aromatic sulfonic acid metal salt; a fluorinated olefin resin; And an inorganic filler having a refractive index difference from that of the polycarbonate resin of about 0 to about 0.01;

In the above formula 1, R ₁ and R ₂ are independently alkyl groups having 1 to 10 carbon atoms;

In the above formula 2, R ₃ and R ₄ are independently alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 12 carbon atoms, _{and at least one of R 3} and R ₄ is an aryl group. Is.

In a specific example, the thermoplastic resin composition comprises about 100 parts by weight of the polycarbonate resin, about 0.01 parts by weight to about 1 part by weight of the siloxane copolymer, and about 0.01 parts by weight of the aromatic sulfonic acid metal salt. It may contain about 5 parts by weight, about 0.01 parts by weight to about 0.4 parts by weight of the fluorinated olefin resin, and about 0.1 parts by weight to about 5 parts by weight of the inorganic filler.

In a specific example, the polycarbonate resin may have a weight average molecular weight (Mw) of about 10,000 g / mol to about 200,000 g / mol.

In a specific example, the siloxane copolymer may have an aryl group content of about 30 mol% to about 50 mol% out of 100 mol% of the total substituents.

In a specific example, the siloxane copolymer may contain one or more of poly (dialkylsiloxane-co-arylalkylsiloxane) and poly (dialkylsiloxane-co-diarylsiloxane).

In a specific example, the viscosity of the siloxane copolymer may be about 1 cSt to about 500 cSt at 25 ° C.

In a specific example, the aromatic sulfonic acid metal salt can be represented by the following formula 3.

In the above formula 3, R ₅ and R ₆ are each independently a hydrocarbon group having 1 to 20 carbon atoms, and M is independently composed of lithium (Li), sodium (Na) or potassium (K), respectively. Yes, m is an integer from 0 to 6, and n is an integer from 1 to 6.

In a specific example, the thermoplastic resin composition may have a flame retardancy of V-0 or higher in a 1.5 mm thick test piece measured by a UL-94 vertical test method.

In a specific example, the thermoplastic resin composition may have a transmittance of about 82% to about 95% of a 1.0 mm thick test piece measured by ASTM D1003.

In a specific example, the thermoplastic resin composition may have a Vicat Softening Temperature (VST) of about 140 ° C. or higher as measured under the conditions of a load of 5 kg and 50 ° C./hr based on ISO R306. ..

Another aspect of the present invention relates to a molded article formed from the thermoplastic resin composition.

The present invention has the effect of providing a thermoplastic resin composition having excellent flame retardancy, transparency, rigidity, heat resistance, and a balance of these physical properties, and a molded product containing the same.

[Best mode for carrying out the invention]
Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention is (A) polycarbonate resin; (B) siloxane copolymer; (C) aromatic sulfonic acid metal salt; (D) fluorinated olefin resin; and (E) inorganic filling. Agent; contains.

(A) Polycarbonate Resin As the polycarbonate resin according to a specific example of the present invention, ordinary thermoplastic polycarbonate resin can be used without limitation. For example, an aromatic polycarbonate resin produced by reacting one or more diphenols (aromatic dihydroxy compounds) with a carbonate precursor such as phosgene, halogen formate, or carbonic acid diester may be used.

In a specific example, the diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1. -Bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, and mixtures thereof. Etc., but are not limited to this. For example, the diphenols include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, and 1,1-bis (4-hydroxyphenyl). ) Cyclohexane or the like may be used, and specifically, 2,2-bis (4-hydroxyphenyl) propane, which is also called bisphenol A, may be used.

The polycarbonate resin may have branched chains, for example, trivalent or more of about 0.05 mol% to about 2 mol% with respect to the total diphenols used for polymerization. It may be produced by adding a polyfunctional compound, for example, a compound having a trivalent or higher phenol group. The polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. It is also possible to replace part or all of the polycarbonate resin with an aromatic polyester-polycarbonate resin obtained by polymerizing in the presence of an ester precursor, for example, a bifunctional carboxylic acid.

In a specific example, the polycarbonate resin has a weight average molecular weight (Mw) of about 10,000 g / mol to about 200,000 g / mol, for example, about 15,000 g, as measured by gel permeation chromatography (GPC). It may be from / mol to about 80,000 g / mol. Within the above range, the processability, mechanical properties, and the like of the thermoplastic resin composition can be excellent.

In a specific example, the polycarbonate resin may have a refractive index of about 1.58 to about 1.59, for example, about 1.581 to about 1.587. Within the above range, the transparency of the thermoplastic resin composition and the like can be excellent.

(B) Siloxane Copolymer The siloxane copolymer according to a specific example of the present invention is a polydialkylsiloxane in which a part of the alkyl group is replaced with an aryl group, and is a repeating unit represented by the following formula 1. And the repeating unit represented by the following formula 2.

In the above formula 1, R ₁ and R ₂ may be independently alkyl groups having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group and the like.

In the above formula 2, R ₃ and R ₄ are independently alkyl groups having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group, or the like, or have a carbon number of carbons. It may be an aryl group of 6 to 12, for example, a phenyl group, a benzyl group, a tolyl group, an o-xysilyl group, an m-xysilyl group, etc., _{and at least one of R 3} and R ₄ is an aryl group.

Generally, polydialkylsiloxane such as polydimethylsiloxane has a low glass transition temperature (Tg) and is used as an impact reinforcing agent for improving low-temperature impact strength of a thermoplastic resin composition. Since the difference in refractive index is large, there is a problem that the transparency is greatly lowered even when a small amount is added. Therefore, the present invention reduces the difference in refractive index from the polycarbonate resin by using a siloxane copolymer containing an aryl group instead of the thermoplastic siloxane, and has excellent transparency, impact resistance, and the like. A plastic resin composition is obtained.

In a specific example, the siloxane copolymer has an aryl group content of about 30 mol% to about 50 mol% out of 100 mol% of _{all substituents (R 1} , R ₂ , R ₃ and R _{4), for example.} It may be from about 35 mol% to about 45 mol%. Within the above range, the transparency, appearance characteristics, impact resistance, etc. of the thermoplastic resin composition can be excellent.

In a specific example, the siloxane copolymer is a poly (dialkylsiloxane-co-arylalkylsiloxane) such as poly (dimethylsiloxane-co-phenylmethylsiloxane); a poly (dimethylsiloxane-co-diphenylsiloxane) or the like. Dialkylsiloxane-co-diarylsiloxane); and combinations thereof. Specifically, in the poly (dialkylsiloxane-co-arylalkylsiloxane), R ₁ and R ₂ of the formula 1 are alkyl groups, R _{3 of the} formula 2 is an aryl group, and R ₄ is an alkyl group. The poly (dialkylsiloxane-co-diarylsiloxane) may be a copolymer, in which R ₁ and R ₂ of the formula 1 are alkyl groups and R ₃ and R _{4 of the} formula 2 are aryl groups. It may be a siloxane copolymer.

In a specific example, the siloxane copolymer may have a viscosity measured at 25 ° C. using an Ubbelohde viscometer of about 1 cSt to about 500 cSt (centistokes), for example, about 4 cSt to about 300 cSt. Within the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, flame retardancy, and the like.

In a specific example, the siloxane copolymer may have a refractive index of about 1.57 to about 1.59, for example, about 1.575 to about 1.585, and the difference in refractive index from the polycarbonate resin may be large. It may be about 0.01 or less, for example, about 0.001 to about 0.01, specifically about 0.002 to about 0.008. Within the above range, the transparency of the polycarbonate resin composition and the like can be excellent.

In a specific example, the siloxane copolymer is about 0.01 parts by weight to about 1 part by weight, for example, about 0.1 parts by weight to about 0.7 parts by weight with respect to about 100 parts by weight of the polycarbonate resin. May be included. Within the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, heat resistance, and the like.

(C) Aromatic Sulfonic Acid Metal Salt The aromatic sulfonic acid metal salt according to a specific example of the present invention reduces the decomposition of the polycarbonate resin during processing, and has flame retardancy and thermal stability of the thermoplastic resin composition. It can improve rigidity and the like, and can be expressed by the following equation 3.

In the above formula 3, R ₅ and R ₆ are independently hydrocarbon groups having 1 to 20 carbon atoms, for example, an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, specifically, Methylene group, ethylene group, propylene group, butylene group, hexylene group, phenylene group, naphthylene group, alkyl-substituted phenylene group, etc., and M is independently lithium (Li), sodium (Na) or potassium (each). K), m is an integer of 0 to 6, and n is an integer of 1 to 6. Here, when m is 0, R ₅ may be, for example, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

In a specific example, the aromatic sulfonic acid metal salt includes a metal salt of diphenylsulfon-3-sulfonic acid, a metal salt of diphenylsulfon-4-sulfonic acid, a metal salt of diphenylsulfon-3,3'-disulfonic acid and the like. A metal salt of diphenylsulfon-3,4'-disulfonic acid or the like may be used.

In a specific example, the aromatic sulfonic acid metal salt may have an average particle size of about 50 μm to about 500 μm, for example, about 150 μm to about 350 μm. Within the above range, the thermoplastic resin composition has excellent thermal stability, flame retardancy, rigidity, and the like, and it is possible to reduce the roughness of the surface of the molded product due to the aggregation of particles with each other.

In a specific example, the aromatic sulfonic acid metal salt is contained in an amount of about 0.01 parts by weight to about 5 parts by weight, for example, about 0.05 parts by weight to about 2 parts by weight, based on about 100 parts by weight of the polycarbonate resin. May be included. Within the above range, the thermoplastic resin composition may have excellent flame retardancy, thermal stability, rigidity, appearance characteristics, and the like.

In a specific example, the siloxane copolymer (B) and the aromatic sulfonic acid metal salt (C) may be contained in a weight ratio (B: C) of about 3: 1 to about 1: 1. Within the above range, the flame retardancy, heat resistance, and the like of the thermoplastic resin composition can be further improved.

(D) Fluorinated Olefin Resin The fluorinated olefin resin according to a specific example of the present invention forms a fiber network in the resin composition when the thermoplastic resin composition is extruded, and heats up during combustion. The dropping phenomenon can be prevented by lowering the melt viscosity of the plastic resin composition and increasing the shrinkage rate. Examples of fluorinated olefin resins include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, and ethylene / tetrafluoroethylene copolymer. , And combinations thereof, etc., but are not limited thereto. For example, polytetrafluoroethylene (trade name: Teflon (registered trademark)) having a particle size of about 0.05 μm to about 1,000 μm and a specific gravity of about 1.2 g / cm ³ to about 2.3 g / cm ^3. May be used.

In a specific example, the fluorinated olefin resin can be produced by using a known polymerization method, and can be produced in an aqueous medium containing a free radical formation catalyst such as sodium, potassium, ammonium peroxydisulfide, for example. ..

In a specific example, the fluorinated olefin resin may be used in an emulsion state or a powder state. The fluorinated olefin resin in the emulsion state is excellent in dispersibility, but the production process is complicated. Therefore, if it can be appropriately dispersed in the powder state, it is preferable to use it in the powder state.

In a specific example, the fluorinated olefin resin is about 0.01 parts by weight to about 0.4 parts by weight, for example, about 0.05 parts by weight to about 0.3 parts by weight with respect to about 100 parts by weight of the polycarbonate resin. It may be included in parts by weight. Within the above range, the thermoplastic resin composition may be excellent in flame retardancy, transparency, processability and the like.

In a specific example, the aromatic sulfonic acid metal salt (C) and the fluorinated olefin resin (D) may be contained in a weight ratio (C: D) of about 0.5: 1 to about 3: 1. Good. Within the above range, the transparency of the thermoplastic resin composition and the like can be further improved.

(E) Inorganic Filler The inorganic filler according to a specific example of the present invention can improve the rigidity of the thermoplastic resin composition without deteriorating the transparency of the polycarbonate resin, and can be used with the polycarbonate resin. The difference in refractive index may be about 0 to about 0.01, for example, about 0 to about 0.008. If the difference in refractive index between the polycarbonate resin and the inorganic filler exceeds about 0.01, the transparency of the thermoplastic resin composition may be significantly reduced. As the inorganic filler, any one known to those skilled in the art can be used without limitation in form and type as long as the difference in refractive index from the polycarbonate resin satisfies the above range.

In a specific example, the inorganic filler may include talc, wollastonite, whiskers, silica, mica, and mixtures thereof. Such inorganic fillers can have cross sections of various shapes such as circular, oval, rectangular and the like.

In a specific example, the inorganic filler may be a fiber type, a plate type, or the like. For example, the fiber type inorganic filler has a cross-sectional diameter of about 5 μm to about 20 μm and a length before processing of about 2 mm to. The plate-shaped inorganic filler may have a cross-sectional diameter of about 1.5 μm to about 10 μm, and the length before processing may be about 2 mm to about 5 mm. Within the above range, the processability of the thermoplastic resin composition becomes excellent, and not only mechanical properties such as rigidity of the molded product but also appearance characteristics can be improved.

In a specific example, the inorganic filler may be one in which the surface is coated with a surface treatment agent in order to increase the bonding force with the polycarbonate resin. Examples of the surface treatment agent include, but are not limited to, silane compounds, urethane compounds, and epoxy compounds.

In a specific example, the inorganic filler is contained in an amount of about 0.1 parts by weight to about 5 parts by weight, for example, about 0.5 parts by weight to about 1.5 parts by weight, based on about 100 parts by weight of the polycarbonate resin. May be. Within the above range, the flame retardancy, transparency, rigidity and the like of the thermoplastic resin composition can be excellent.

The thermoplastic resin composition according to a specific example of the present invention may further contain ordinary additives, if necessary. Examples of the additive include flame retardants, flame retardant aids, antioxidants, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof. Not limited. The content of the additive may be, but is not limited to, about 0.01 parts by weight to about 20 parts by weight with respect to about 100 parts by weight of the polycarbonate resin.

The thermoplastic resin composition according to a specific example of the present invention may have a flame retardancy of V-0 or more in a 1.5 mm thick test piece measured by the UL-94 vertical test method.

In a specific example, the thermoplastic resin composition may have a transmittance of about 82% to about 95%, for example, about 82% to about 90% of a 1.0 mm thick test piece measured by ASTM D1003. ..

In a specific example, the thermoplastic resin composition has a Vicat Softening Temperature (VST) of about 140 ° C. or higher, for example, about 143, measured under the conditions of a load of 5 kg and 50 ° C./hr based on ISO R306. The temperature may be from ° C to about 160 ° C.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition of the present invention can be produced by a known method for producing a thermoplastic resin composition. For example, the constituent components are mixed with other additives if necessary, and then an extruder is used. It can be produced in the form of pellets, chips, etc. by melting and extruding. The produced thermoplastic resin composition such as pellets and chips can be produced into various molded products (products) through molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such a molding method is well known to those who have ordinary knowledge in the field to which the present invention belongs. The molded product has excellent flame retardancy even if it is thin, and has excellent transparency, rigidity, heat resistance, and a balance of these physical properties, and is therefore useful for automobile parts, electrical / electronic product parts, exterior materials, and the like. is there.

[Mode for carrying out the invention]
Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred examples of the present invention. However, this is presented as a preferred example of the present invention and should not be construed as limiting the present invention in any way.

The specifications of each component used in the examples and comparative examples below are as follows:
(A) Polycarbonate Resin A bisphenol-A type polycarbonate resin (refractive index: 1.583, weight average molecular weight: 25,000 g / mol) was used.

(B) Siloxane copolymer poly (dimethylsiloxane-co-diphenylsiloxane) (manufacturer: GE Toshiba Silicone Co., Ltd., product name: TSF-437, refractive index: 1.58 (theoretical value), viscosity: 22 cSt) used.

(C) Aromatic sulfonic acid metal salt A potassium salt of diphenylsulfon-3-sulfonic acid (potassium diphenyl sulfone-3-sulfonate, manufacturer: Seal Sands Chemicals Co., Ltd., product name: KSS) was used.

(D) Fluorinated olefin resin polytetrafluoroethylene (manufacturer: DuPont, product name: CFP 614A) was used.

(E) Inorganic filler (E1) Talc having a refractive index of 1.58 (manufacturer: Hayashi Kasei Co., Ltd., product name: HS-T 0.5) was used.
(E2) Kaolin having a refractive index of 1.533 (manufacturer: Australian China Clays Limited, product name: Microbrite C80 / 95 C1) was used.

[Examples 1 to 4 and Comparative Examples 1 to 3]
According to the composition and content in Table 1 below, the components were mixed in a tumbler mixer for 10 minutes and then added to a twin screw type extruder having L / D = 44 and a diameter of 45 mm, and the temperature was adjusted to 240 ° C. to A thermoplastic resin composition in the form of chips was produced by melting and extruding under the conditions of 300 ° C. and a stirring speed of 250 rpm. The manufactured chip is dried at 80 ° C. for 5 hours or more, and then injection-molded at 240 ° C. to 300 ° C. with a screw-type injection machine (manufacturer: LG electric wire, product name: LGH-140N) to form a test piece. Manufactured. The physical properties of the manufactured test pieces were evaluated by the following methods, and the results are shown in Table 1 below.

Physical property measurement method (1) Flame retardancy evaluation: The flame retardancy of a test piece having a thickness of 1.5 mm was measured by the UL9-4 vertical test method.
(2) Transparency (Unit:%): Based on ASTM D1003, the transmittance of a 1.0 mm thick test piece was measured with a Haze Meter (YDP02-0D) manufactured by Nippon Denshoku Industries Co., Ltd.
(3) Heat resistance evaluation: Based on ISO R306, the Vicat Softening Temperature (VST) (unit: ° C.) was measured under the condition of a load of 5 kg and 50 ° C./hr.

From the above results, it can be seen that the thermoplastic resin composition according to the present invention is excellent in flame retardancy, transparency, heat resistance, and a balance of these physical properties.

On the other hand, in the case of Comparative Example 1 using an inorganic filler having a refractive index difference of more than 0.01 from the polycarbonate resin, it was found that the transparency and flame retardancy were lowered, and an aromatic sulfonic acid metal salt was used. It can be seen that in the case of Comparative Example 2 in which the inorganic filler is not used and Comparative Example 3 in which the inorganic filler is not used, the flame retardancy is significantly reduced.

Simple modifications and modifications of the present invention can be easily carried out by a person having ordinary knowledge in the art, and any such modifications or modifications can be considered to be included in the domain of the present invention. ..

Claims (9)

Polycarbonate resin;
A siloxane copolymer containing a repeating unit represented by the following formula 1 and a repeating unit represented by the following formula 2;
Aromatic sulfonic acid metal salt represented by the following formula 3;
Fluorinated olefin resin; and the difference in refractive index from the polycarbonate resin is 0 to 0 . 01 a is an inorganic filler; only including,
The thermoplastic resin composition characterized in that the viscosity of the siloxane copolymer is 1 cSt to 500 cSt at 25 ° C .:

In the above formula 1, R ₁ and R ₂ are independently alkyl groups having 1 to 10 carbon atoms;

In the above formula 2, R ₃ and R ₄ are independently alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 12 carbon atoms, and _{at least one of R 3} and R ₄ is an aryl group. Yes ;

In the above formula 3, R ₅ and R ₆ are independently arylene groups having 6 to 20 carbon atoms, and M is independently lithium (Li), sodium (Na) or potassium (K), respectively. , M is an integer of 0 to 6, and n is an integer of 1 to 6 . The thermoplastic resin composition, the polycarbonate resins 1 00 parts by weight, the copolymer 0. 01 parts by weight to 1 part by weight, said aromatic sulfonic acid metal salt 0 . 01 to 5 parts by weight, the fluorinated olefin resins 0. 01 parts by weight to 0 . 4 parts by weight and the inorganic filler 0 . The thermoplastic resin composition according to claim 1, which comprises 1 part by weight to 5 parts by weight. The thermoplastic resin composition according to claim 1, wherein the polycarbonate resin has a weight average molecular weight (Mw) of 10,000 g / mol to 200,000 g / mol. The thermoplastic resin composition according to claim 1, wherein the siloxane copolymer has an aryl group content of 30 mol% to 50 mol% out of 100 mol% of the total substituents. The thermoplastic according to claim 1, wherein the siloxane copolymer contains one or more of poly (dialkylsiloxane-co-arylalkylsiloxane) and poly (dialkylsiloxane-co-diarylsiloxane). Resin composition. The thermoplastic resin according to claim 1, wherein the thermoplastic resin composition has a flame retardancy of V-0 or more for a test piece having a thickness of 1.5 mm measured by a UL-94 vertical test method. Composition. The thermoplastic resin composition is characterized by 1.0mm permeability in the thickness of the specimen measured by ASTM D1003 is 82% to 9 5%, the thermoplastic resin composition of claim 1 .. The thermoplastic resin composition is characterized in that 5kg load based on ISO R306, Vicat softening temperature was measured under conditions of 50 ° C. / hr is 1 40 ° C. or more, thermoplastic of claim 1 Resin composition. A molded product formed from the thermoplastic resin composition according to any one of claims 1 to 8.